Halogenated dibenzanthrones



Patented Nov. 27, 1934 UNITED STATES PATENT OFFICE 1,982,313 I HALOGENATED DIBENZANTHRONES Max Albert Kunz, Mannheim, and Karl-Koeberlc and. Erich Berthold, Ludwigshafen-on-the- Rhine, Germany, assignors to General Aniline Works, linc., New York Delaware N. Y., a corporation of No Drawing. Application April 14, 1931, Serial No. 530,140. In Germany April 27, 1929 4 Claims.

.10 the halogen derivatives produced according to the methods heretofore proposed with respect to the dyeings obtained therewith and especially with respect to their fastness to spotting with water, are obtained by halogenating derivatives ,1; of dibenzanthrone in an organic diluent by means of anhydrous metal halides supplying halogen, if desired in conjunction with a further halogenating agent, such as for example free halogen, or agents supplying halogen, such as sulphuryl chloride, iodine chloride and the like.

As examples of metal halides which are especially suitable for carrying out the process according to the present invention may be mentioned the halides of iron, aluminium, antimony, mercury and the like and mixtures of these halides. As diluents which may be used according to our invention there may be mentioned halogen benzenes, halogen naphthalenes, benzophenone, nitrobenzene, quinoline, pyridine and collidine. Halogenating catalysts, for example metals or compounds thereof, or non-metals, for example iodine, sulphur or compounds thereof may be added to the reaction mixture.

In order to produce halogenated isodibenzanthrones fast to spotting with water, halogen and more particularly chlorine is introduced into the isodibenzanthrone molecule to such an extent that from 3 to 6, preferably from 3 to 5, and most suitably from 3 to 4, halogen atoms, in particular chlorine atoms are present per molecule; These products may also be obtained by carrying out the halogenation, in particular chlorination, in organic diluents by means of other halogenating agents than metal halides supplying halogen; The process making use of metal halides as the halogenating agents may be employed for the further halogenation of dibenzanthrones already containing halogen by introducing either further amounts of the halogen already present or a dif ierent halogen. Other derivatives of dibenzanthrone may also advantageously be halogenated by that process, for example nitro, amino, hy droxy, alkoxy and alkyl derivatives.

The following examples will further illustrate the nature'of this invention, but the invention is not restricted thereto.

Example 1 62 parts of dibromdibenzanthrone, prepared by bromination of dibenzanthrone in chlorsulphonic acid, are heated to 140 C. in 2000 partsoi" trichlorbenzene while stirring. 480 parts of anhydrous iron chloride are introduced at this .tem- 65 perature and the reaction mixture is stirred at from 140 to 150 C. until a sample taken out yields a green-blue vat solution from which -cotton isdyed shades which are fast to water. The reaction mixture is then allowed to cool and the trichlorbenzene is distilled off if desired with steam and/or under reduced pressure. The reaction product, which is obtained 'in excellent yields, dissolves in concentrated sulphuric acid giving a violet colouration and is a chlorbromdibenzanthrone. The navy-blue dyeings obtainable therewith from a green-blue vat have, in addition to very good general properties, the advantage, contrasted with the initial material that the shade is independent of the dyeing temperature. In spite of the introduction of chlorine the shade is changed towards green-and moreover the dyeings have a fastness to drops ofwater which satisfies all practical requirements, 1. e. they do not change to red when spotted with 5 water. The crude dyestuii may be crystallized from organic solvents as for example nitrobenzone or from sulphuric acid, or may be purified by other methods as for example by treatment in the form of paste with oxidizing agents such as sodium hypochlorite.

The dyestufi may be converted into its leuco ester or into other leuco preparations-according to the usual methods.

behaviour to the reaction product obtained according to Example 1.

A similar dyestufi is obtained by the action of no a 100 parts of iron chloride or less iron chloride than stated above.

Example 3 parts of brominated dibenzanthrone (prepared from pure dibenzanthrone by bromination in nitrobenzene) are heated to 140 C. in 1500 parts of trichlorbenzene, 110 parts of anhydrous iron chloride then being added at this temperature. The reaction mixture is then stirred at from 140 to 150 C. until a sample taken'out gives a green-blue vat and yields navy blue dyeings fast to water. The reaction mixture is then worked up as described in Example 1. The chlorbromdibenzanthrone, which is obtained in excellent yields, dissolves in concentrated sulphuric acid giving a violet colouration, it gives a greenblue vat and yields navy blue dyeings having excellent fastness on the vegetable fibre.

The preparation of the brominated dibenzanthrone and the further treatment of the same with iron chloride may also be carried out in one operation.

By treating isodibenzanthrone in trichlorbenzene with bromine and iron chloride a reaction product is obtained in an analogous manner which contains chlorine and bromine and which yields violet dyeings fast to drops of water and having very good fastness on cotton from greenblue vat.

Example 4 440 parts of anhydrous iron chloride are added while stirring at 140 C. to 62 parts of dibromisodibenzanthrone (prepared by bromination of pure isodibenzanthrone in an acid medium in chlordibromisodibenzanthrone is a violet powder which dissolves in concentrated sulphuric acid giving a green colouration and dyes cotton from a green blue vat clear powerful violet shades hav ing very good fastness which practically no longer change to red when spotted with water.

Chlorbrom derivatives of isodibenzanthrone which give violet dyeings are obtained in an analogous manner from monobromisodibenzanthrone or tri-, tetraand penta-bromisodibenzanthrone.

Example 5 a tetrabromdibenzanthrone containing chlorine,

dissolves in concentrated sulphuric acid giving a violet colouration and yields blue dyeings of 'excellent fastness on cotton.

In an analogous manner products containing more chlorine are obtained from dichlordibenzanthrone and reaction products containing chlorine and iodine are obtained from icdodibenzanthrone.

Example 6 42.5 parts of tetrabrom-dichlordibenzanthrone (prepared from dibenzanthrone by brominating in chlorsulphonic acid in the presence of sulphur) are heated to 100 C. in 1000 parts of trichlorbenzene while stirring. After the addition of 240 parts of iron chloride the temperature is raised to from 145 to 150 centigrade and is kept constant for several hours. The reaction mixture is then allowed to cool and is worked up as described in Example 1. The reaction product, which is obtained in excellent yields, dyes substantially more greenish shades than the initial material. It dissolves in concentrated sulphuric acid to give a violet colouration.

Example 7 31 parts of dibromdibenzanthrone (prepared as described in Example 1) are boiled for several hours while stirring in 1000 parts of dichlorben- Zene with 100 parts of mercury chloride. After cooling, the reaction mixture is worked up as described in Example 1. The reaction product containing chlorine is a violet-blue powder, it dissolves in concentrated sulphuric acid giving a violet colouration and yields navy blue dyeings fast to drops of water and having very good fastness on cotton from a green-blue vat.

A mixture of iron chloride and mercury chloride may be employed equally well instead of mercury chloride.

Dichlorbenzene may be replaced by other solvents or suspending agents as for example monochlorbenzene, trichlorbenzene or nitrobenzene.

Example 8 46 parts of pure dibenzanthrone are heated for two hours to from 140 to 150 C. in 1000 parts of trichlorbenzene after the addition of 2 parts of iodine and 32 parts of bromine. 240 parts of iron chloride are then added and the reaction mixture is kept at the same temperature for several hours. When the reaction is completed the reaction mixture is allowed to cool and is worked up as described in Example 1. The resulting dyestuff, which is a blue powder, dissolves in concentrated sulphuric acid giving a violet colouration, it yields a green-blue vat and has tinctorial properties similar to those of the reaction product described in Example 1. Instead of trichlorbenzene, nitrobenzene may equally well be used as the diluent.

Example 9 d3 parts of pentabromdibenzanthrone (prepared from dibenzanthrone by bromination in chlorsulphonic acid in the presence of a metallic catalyst) are heated in 1000 parts of trichlorbenzene with 250 parts of antimony pentachloride for several hours at from 80 to 100 C. while stirring, and the reaction mixture is worked up in the usual manner after being cooled. The resulting dyestuff, which is a chlorpentabromdibenzanthrone, dissolves in concentrated sulphuric acid only with difiiculty to give a violet colouration; it yields a green-blue vat and dyes cotton very fast blue shades.

Example 10 39 parts of tetrabromisodibenzanthrone are suspended in 1000 parts of nitrobenzene, and 240 parts of iron chloride are added to the suspension at C. while stirring. The reaction mixture is then stirred for several hours at from to C., allowed to cool, and the chlorine-containing reaction product formed is isolated as described in Example 1. It is a blue powder Which dissolves in concentrated sulphuric acid to give a violet colouration, it yields a green-blue vat and dyes cotton excellently fast navy blue shades.

Example 11 A suspension of 31 parts of dibromdibenzanthrone (prepared as described in Example 1) in 300 parts of collidine are heated While stirring to 120 centigrade, 240 parts of iron chloride are introduced, the temperature is raised to 150 C. and is kept constant for several hours. When a sample taken out yields dyeings similar to those of the dyestufi obtainable according to Example 1, the reaction mixture is allowed to cool and is worked up in the usual manner. The dyestuff which is obtained in excellent yields in the form of a blue powder dissolves in concentrated sulphuric acid giving a violet colouration and yields navy blue dyeings fast to drops of water and having very good fastness on cotton from a greenblue vat.

Example 12 parts of dibromdibenzanthrone (prepared as described in Example 1) are suspended in 200 25 parts of trichlorbenzene and heated to 140 centigrade while stirring. 100 parts of iron chloride and parts of iron bromide are then added thereto and the reaction mixture is stirred for several hours at from 140 to 150 centigrade, allowed to cool and worked up in the manner Example 13 While stirring at from 130 to 140 C., 100 parts of iron chloride are introduced into a suspension of 20 parts of bromnitrodibenzanthrone (prepared by brominating nitrodibenzanthrone in nitrobenzene in the presence of iron) in 200 parts of trichlorbenzene. After the reaction mixture has been stirred for from 2 to 3 hours at from 120 to 130 C., it is allowed to cool and is worked up in the usual manner. The dyestuff thus obtained in the form of a blue powder, a chlorbromnitrodibenzanthrone, dissolves in concentrated sulphuric acid giving a red-violet colouration and dyes cotton from a blue vat fast navy blue shades.

Example 14 reaction mixture is then further heated at be tween 120 and 130 C. for a short time and worked up as usual. The chlorobromaminodibenzanthrone thus obtained dissolves in concentrated sulphuric acid giving a blue-violet solution 4 and dyes cotton strong grey shades from a greenish-blue vat.

Example 15 25 parts of bromnitroisodibenzanthrone ob- 1 tainable by brominating nitroisodibenzanthrone in nitrobenzene at 160 C. are treated in trichlorobenzene with iron chloride and worked up as described in the foregoing example. The chlorobromnitroisodibenzanthrone thus obtained is a violet powder, dissolves in concentrated sulphuric acid to give a green solution and dyes cotton from a blue vat strong reddish blue shades.

Example 16 dyes cotton from a blue vat fast reddish blue shades.

' Example 17 46 parts of pure isodibenzanthrone are heated for from 5 to 6 hours to between and C. in 1-60 parts of nitrobenzene with an addition of 5 parts of ferric chloride, while introducing a current of chlorine. When a sample taken out has a chlorine content of 22 per cent or more, the reaction mass is allowed to cool and the product which has separated in a crystalline state is filtered ofi by suction. It dissolves in anhydroussulphuric acid giving an olive green solution and dyes the vegetable fibre from a greenish blue vat violet shades which do not change to a more reddish tinge when spotted with water.

Similar results are obtained when employing antimony pentachloride or aluminium chloride instead of ferric chloride.

Example 18 92 parts of isodibenzanthrone are mixed gradually in 2000 parts of trichlorobenzene at between 80 and 100 C. with 650 parts of ferric chloride, whereupon the reaction mixture is heated for several hours to between 145 and 150 C. until the reaction is complete, as results from the disengagement of hydrochloric acid ceasing practically completely. The reaction mass is worked up in the usual manner. The resulting chloro derivative of isodibenzanthrone which contains from 4 to 5 atoms of chlorine per molecule, is similar in its properties to the reaction product described in Example 17.

A reaction product dyeing similar shades is obtained by heating isodibenzanthrone in nitro benzene with from 5 to 6 parts of antimony pentachloride.

Example 19 52 parts of 6,6-dichloroisodibenzanthrone are heated for a short time to 175 C.,in 700 parts of nitrobenzene with an addition of 200 parts of antimony pentachloride while stirring, whereupon the temperature is increased for some time to 195 C., and finally the mass is boiled for a short time. which an excellent yield is obtained, is filtered off by suction. It is in the form of crystalline needles having a bronze lustre which dissolve in fuming sulphuric acid giving a green solution and which dye the vegetable fibre from a blue vat strong violet blue shades which do not become more reddish when spotted with water.

Similar reaction products are obtained in this manner from other synthetically prepared isodibenzanthrones or from isodibenzanthrones prepared by direct chlorination for example in chlorosulphonic acid or. in nitrobenzene and containing less than 3 atoms of chlorine per molecule.

Example 20 62 parts of dibromo-isodibenzanthrone obtainable by brominating isodibenzanthrone are slow- After cooling, the reaction product of ly heated to 200 C. in 600 parts of nitrobenzene together with 250 parts of antimony pentachloride; the reaction mass is kept for several hours at the said temperature, and after cooling the product is Worked up in the usual manner. The resulting product containing chlorine and bromine is a violet blue powder which dissolves in concentrated sulphuric acid giving a green solution and which dyes the vegetable fibre from a greenish blue vat bluish violet shades which are not substantially altered when spotted with Water.

This application is a continuation in part of our copending application Ser. No. 447,108, filed April 24, 1930.

What we claim is:

1. The process of producing chloroisodibenzanthrones which comprises treating 6,6'-dichloroisodibenzanthrone with antimony pentachloride in nitrobenzene at a temperature between 175 C. and the boiling point of the solution, until the reaction product contains at least 3 atoms of chlorine per molecule.

2. Chlorinated isodibenzanthrones which contain between 3 and 6 atoms of chlorine er molecule, of which chlorine atoms two are in the 6 and 6' positions, and which dye the vegetable fibre violet shades which do not become substantially more reddish when spotted with water.

3. Chlorinated isodibenzanthrones which contain between 3 and 6 atoms of chlorine per molecule, of which chlorine atoms two are in the 6 and 6 positions, and which dye the vegetable fibre violet shades which do not become more reddish when spotted with water, the said products being obtainable by heating 6,6-dichloroisodibenzanthrone with antimony pentachloride in nitrobenzene at temperatures between 175 C. and the boiling point of the solution.

' 4. Chlorinated isodibenzanthrones which contain between 3 and 4 atoms of chlorine per moleoule, dissolve in anhydrous sulphuric acid giving an olive green solution and dye the vegetable fibre from a greenish blue vat violet shades which do not become more reddish when spotted with water, said products being obtainable by heating pure isodibenzanthrone in nitrobenzene with ferric chloride and chlorine to between 95 and MAX ALBERT KUNZ.

KARL KOEBERLE. ERICH BERTHOLD. 

